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Abstract: Vanadium oxide supported on mesoporous zirconium phosphate catalysts has been synthesized, characterized and tested in the selective oxidation of H2S to sulfur. The nature of the vanadium species depends on the V-loading of catalyst. Catalysts with a V-content lower than 4wt% present both isolated vanadium species and V2O5 crystallites. However, V2O5 crystallites have been mainly observed in catalysts with higher V-content, although the presence of isolated V-species on the surface of the metal oxide support cannot be completely ruled out. The catalytic behaviour also depends on V-loading of catalysts. Thus, while the catalytic activity of catalysts can be related to the number of V-sites, the catalyst decay is clearly observed in samples with low V-loading. The characterization of catalysts after the catalytic tests indicates the presence of sulfur on the catalyst, which is favoured on catalysts with low V-loading. However, a clear transformation of V2O5 to V4O9 can be proposed according to XRD and Raman results of used catalysts with high V-loading. The importance of V5+–O–V4+ pairs in activity and selectivity is also discussed. [Copyright &y& Elsevier]